EP0401063B1 - Polymere mit nichtlinearer optischer Aktivität - Google Patents

Polymere mit nichtlinearer optischer Aktivität Download PDF

Info

Publication number
EP0401063B1
EP0401063B1 EP90401164A EP90401164A EP0401063B1 EP 0401063 B1 EP0401063 B1 EP 0401063B1 EP 90401164 A EP90401164 A EP 90401164A EP 90401164 A EP90401164 A EP 90401164A EP 0401063 B1 EP0401063 B1 EP 0401063B1
Authority
EP
European Patent Office
Prior art keywords
polymer according
radical
diisocyanate
polymer
aromatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90401164A
Other languages
English (en)
French (fr)
Other versions
EP0401063A1 (de
Inventor
Pascal Barthélémy
Gérard Mignani
Rémi Meyrueix
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Flamel Technologies SA
Original Assignee
Flamel Technologies SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Flamel Technologies SA filed Critical Flamel Technologies SA
Publication of EP0401063A1 publication Critical patent/EP0401063A1/de
Application granted granted Critical
Publication of EP0401063B1 publication Critical patent/EP0401063B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3836—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing azo groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3838—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing cyano groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/384—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing nitro groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/679—Acetylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers
    • G02F1/3617—Organic materials containing polymers having the non-linear optical group in a side chain
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention relates to polymers active in non-linear optics.
  • It relates more particularly to a high molecular weight polymer having a high concentration of active units in non-linear optics, or hyperpolarisables.
  • organic materials generally consist of a polymerizable matrix in which a hyperpolarizable organic compound is dissolved or incorporated.
  • these materials have certain drawbacks, mainly due to the solubility and compatibility of the organic compound in the matrix.
  • Polymerized organic materials have also been proposed comprising hyperpolymerizable groups grafted onto the main chain of the polymer via more or less long hydrocarbon chains.
  • the conjugated monomer may be a diisocyanate.
  • the hyperpolarisable group is part of the main chain or backbone of the polymer. Consequently, the residual mobility of these groups is zero, if not very low since it requires mobility of the polymer chain.
  • chain extenders such as diols (recurring motif B). It should be recalled that for a compound to have a quadratic ONL activity, it is also necessary that the compound has a good ability to be oriented by means of an electric field and to keep this orientation.
  • the active materials in nonlinear optics are generally used as a film in optical devices or optoelectronic, these films to be as regular as possible and small thickness (a few tens of micron, 10- 2 to 10- 1 mm).
  • the materials described above have the major drawback of being weakly film-forming and poorly soluble in the solvents usually used to make films such as, dichloromethane, dimethylformamide (DMF), N-methyl pyrolidone (NMP), chloroform, cyclohexanone, methyl isobutyl ketone.
  • the nitro and cyano groups are preferred.
  • the aromatic groups Zi, Z 2 are chosen from phenylene, biphenylene, naphthylene groups,
  • the preferred radicals R 7 are moderately bulky radicals, that is to say that they correspond to the bulk of an isopropyl or isoamyl.
  • R 7 When R 7 is located on the Z 1 group, it is advantageously a donor while when it is located on Z 2 , it is advantageously an acceptor.
  • lower alkyl radical is meant linear or branched aliphatic radicals comprising from 1 to 6 carbon atoms.
  • the preferred R 7 radicals of the invention are the methyl and ethyl radicals.
  • the molecular weight M n of the material of the invention is between 1000 and 15000 while M w is between 3000 and 100000.
  • the radical R 3 is a hydrocarbon residue of the diisocyanate compound used as a monomer for the formation of the material.
  • diisocyanates examples include hexamethylene diisocyanate (HDI), diphenyl ether diisocyanate (DIDE), diphenyl methylene diisocyanate (MDI) or naphthyl diisocyanate.
  • HDI hexamethylene diisocyanate
  • DIDE diphenyl ether diisocyanate
  • MDI diphenyl methylene diisocyanate
  • naphthyl diisocyanate examples include hexamethylene diisocyanate (HDI), diphenyl ether diisocyanate (DIDE), diphenyl methylene diisocyanate (MDI) or naphthyl diisocyanate.
  • aromatic isocyanates and in particular diphenyl methylene diisocyanate gives particularly good results, in particular as regards the absence of relaxation of the polarization over time.
  • the preferred polymers of the invention have the recurring motif of the following formula:
  • These materials have better solubility in solvents and can therefore be easily shaped in particular for the production of a film or a coating and is easily oriented in an electric field during the production of the film.
  • collodion On a glass plate covered with a transparent conductive layer at the wavelength to be used, collodion whose viscosity is adjusted to a value between 1 / 2.10- 2 and 1 / 4.10 to 3, preferably from 50 to 200 centipoises by addition or evaporation of solvents and filmed with "Mayer's bar" and this using a film-drawing device such as for example that sold under the trade name K control coater of the motorized Erichsen brand.
  • the film thus obtained is gradually dried up to a temperature at most close to the glass transition temperature (tg); the film is then dried under vacuum at a temperature close to that of the glass transition for 24 hours.
  • a second conductive layer is deposited and two electrodes are deposited on the conductive layers.
  • the conductive layers are either gold or various conductive oxides, such as tin oxide or mixed oxides of tin and indium.
  • the polarization is carried out at a temperature at most equal to the ending glass transition temperature preferably close to the starting glass transition temperature.
  • the bias voltage is applied between the two layers of gold. This voltage is chosen between 1 and 100 volts per micro / meter ( ⁇ m). It is however difficult and rare to obtain this behind value because films tend to snap under a strong potential difference, this is the reason why a voltage between 10 and 50 volts per micro meter is more commonly used, more generally still between 20 and 30 v / ⁇ m.
  • This bias voltage may be slightly lower than the initial bias voltage.
  • the polymers according to the present invention have shown great inclinations to be polarized and to maintain this polarization over time.
  • the glass transition temperatures of these materials are higher than those of materials containing no substituents, and therefore have better mechanical properties and above all good preservation of the optical properties during aging.
  • the presence of the substituents modifies the electronic structure of the molecule and promotes the shape of the molecule which allows better electronic delocalization and therefore increases the hyperpolarisibility of the molecules.
  • These polymers are used in particular in optical and optoelectric devices such as, for example, switches, modulators, directional couplers, bistable.
  • the presence of the substituents modifies the electronic structure of the molecule.
  • the electron donor substituents such as the alkyl radicals carried by the radical Z 1 make it possible to increase the max, on the contrary the electro-accepting substituents such as the halogens carried by the radical Z 1 reduce the ⁇ max (see the article published by JBDickey and AI in Am. Dyestuff reporter (1965) page 44).
  • a dilute solution of strong acid (HCl or H 2 SO 4 type ) is introduced into a reactor; 50% W; we then add an equivalent of aniline (for example: , ....); after complete dissolution, it is cooled to -5 ° C. (using ice water) and then an equivalent of NaN0 2 is added in the minimum amount of water.
  • We then add the compound to be copulated in general It is left to react for 1 hour to 2 hours at room temperature.
  • a type compound can be prepared via a condensation reaction or even in particular: theme on the synthesis of styblene.
  • This reaction is carried out at 90 ° C for 4 hours.
  • the reaction mass is poured into 2 liters of water.
  • the precipitate obtained is filtered, washed with water and then dried.
  • the glass transition temperature measured on the plug pendulum is 77 ° C.
  • the structure of the polymer determined by differential thermal analysis (ATD) is amorphous, its formula is confirmed by spectral analyzes.
  • NMP N-methylpyrolidone
  • Example 1 is repeated, using dimethyl formamide (DMF) in place of DMEU as solvent, the diisocyanate (HDI) and the diol (see formula in example 1) being reacted in equimolar amounts.
  • DMF dimethyl formamide
  • HDI diisocyanate
  • HDI diisocyanate
  • the structure of this polymer is also amorphous and the ⁇ max (NMP) is equal to 500 nm.
  • Example 1 is repeated but using as diol the compound of the following formula (the diol / isocyanate molar ratio being equal to 1):
  • Example 1 is repeated taking as diol, the compound of the following formula (the diol / diisocyanate molar ratio being equal to 1%
  • NMP NMP
  • Example 4 is repeated but using as diisocyanate instead of hexamethylene diisocyanate, diphenyl ether diisocyanate (DIDE).
  • DIDE diphenyl ether diisocyanate
  • NMP maximum wavelength
  • Example 4 is repeated but without using a catalyst (DLDBE).
  • the polymer obtained has the formula:
  • I ⁇ has a glass transition temperature Tg equal to 83 ° C and has a maximum adsorption wavelength ( ⁇ max) in the NMP of 462 nm.
  • Example 1 is repeated, but using the following diisocyanate instead of HDI:
  • the polymer obtained has a glass transition temperature Tg equal to 135 ° C, a max (NMP) equal to 502 nm.
  • the susceptibility x 2 is measured at frequencies (-w; w, o) in an electrooptical experiment.
  • the film is deposited on a glass slide covered with a transparent conductive oxide (Sn0 2 ).
  • the outer face of the film is covered by a semi-transparent gold layer, the oxide and the gold serving as electrodes by which n polarizes the film to make it non-centrosymmetric.
  • the assembly is placed in one of the arms of a MACH ZENDER interferometer and traversed under normal incidence by a laser beam of wavelength equal to 633 nm.
  • the film is then subjected to an alternating voltage of 1 KHz and 10V.
  • Quadratic susceptibility is deduced from the phase delay ⁇ caused by the voltage applied to the film by the following relation:
  • the second susceptibility coefficient is given by the relation
  • the film was produced from a solution in cyclohexanone of the polymer of Example 4, the solution containing 10% of dry extract.
  • the film produced has a thickness of 6.3 ⁇ m after drying at 110 ° C. under vacuum and is polarized under an electric field of 30 volts per micron at a temperature of 100 ° C. for 60 seconds.
  • the quadratic susceptibility ⁇ 2 333 measured is equal to 80 ⁇ 10 -12 m.volt -1 .
  • This susceptibility is very high for a relatively weak polarization field.
  • HDI-HDT mixture is poured 4.95 g of HDI-HDT mixture (molar%) or 0.0576 mole of NCO function (5.1% excess).
  • the mass obtained is introduced into 500 ml of water with very vigorous stirring; the precipitate obtained is washed three times with water and dried under vacuum; 14.4 g of a red solid are thus obtained; the yield is almost quantitative.
  • the infrared, ultraviolet and NMR analyzes of the proton confirm the structure of the polymer.
  • the infrared, ultraviolet and NMR analyzes of the proton confirm the structure of the polymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Emergency Medicine (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Medical Uses (AREA)
  • Indole Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Claims (12)

1. Polymere, dadurch gekennzeichnet, daß sie im wesentlichen aus wiederkehrenden Einheiten folgender Formel bestehen:
Figure imgb0052
in der bedeuten:
- Ri, R2, die gleich oder verschieden sein können, eine geradkettige oder verzweigte Methylenkette mit 2 bis 6 C-Atomen,
- R3 eine aliphatische, aromatische oder araliphatische Kohlenwasserstoffgruppe,
- R4, Rs, die gleich oder verschieden sein können, ein Stickstoffatom oder die Gruppe CH oder zwei Kohlenstoffatome, wobei die Bindung R4-Rs eine Dreifachbindung ist,
- Z1, Z2, die gleich oder verschieden sein können, eine aromatische Gruppe, die mindestens einen Substituenten R7 aufweist, der von der Gruppe A verschieden ist, und die unter geradkettigen und verzweigten aliphatischen Gruppen mit 1 bis 6 C-Atomen ausgewählt ist, und
- A eine Elektronenakzeptorgruppe, vorzugsweise vom Cyano- oder Nitro-Typ, wobei die Gruppe Z2 mehrere Gruppen A aufweisen kann.
2. Polymere nach Anspruch 1, dadurch gekennzeichnet, daß die aromatischen Gruppen Z1, Z2 unter Phenylen, Biphenylen und Naphthylen ausgewählt sind.
3. Polymere nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Substituent R7 Methyl oder Ethyl ist.
4. Polymere nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie ein Zahlenmittel des Molekulargewichts Mn von 1 000 bis 15 000 und ein Gewichtsmittel des Molekulargewichts Mw von 3 000 bis 100 000 aufweisen.
5. Polymere nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Gruppe R3 ein Kohlenwasserstoffrest einen Diisocyanats ist.
6. Polymere nach Anspruch 5, dadurch gekennzeichnet, daß das Diisocyanat unter Hexamethylendiisocyanat, Diphenyletherdiisocyanat, Diphenylmethylendiisocyanat und Naphthyldiisocyanat ausgewählt ist.
7. Polymere nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie mindestens eine wiederkehrende Einheit einer der nachstehenden Formeln aufweisen:
Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056
8. Polymere nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie in Form von Filmen verwendet sind, deren Dipolorientierung so ist, daß cose mindestens gleich 10-2 ist.
9. Polymere nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie in Form eines Überzugs verwendet sind.
10. Vorrichtung, die mindestens ein Element mit nichtlinearen optischen Eigenschaften enthält, dadurch gekennzeichnet, daß dieses Element aus einem Polymer nach einem der Ansprüche 1 bis 7 besteht.
11. Verfahren zur Polarisation eines Polymers nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß Material bei einer Temperatur im Bereich zwischen dem Beginn und dem Ende des Glasübergangs einem elektrischen Feld von 1 bis 100 V/um ausgesetzt wird.
EP90401164A 1989-05-03 1990-04-27 Polymere mit nichtlinearer optischer Aktivität Expired - Lifetime EP0401063B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8905870A FR2646671B1 (fr) 1989-05-03 1989-05-03 Materiau organique actif en optique non lineaire
FR8905870 1989-05-03

Publications (2)

Publication Number Publication Date
EP0401063A1 EP0401063A1 (de) 1990-12-05
EP0401063B1 true EP0401063B1 (de) 1994-11-02

Family

ID=9381383

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90401164A Expired - Lifetime EP0401063B1 (de) 1989-05-03 1990-04-27 Polymere mit nichtlinearer optischer Aktivität

Country Status (9)

Country Link
US (1) US5075409A (de)
EP (1) EP0401063B1 (de)
JP (1) JPH0832760B2 (de)
AT (1) ATE113623T1 (de)
CA (1) CA2015923A1 (de)
DE (1) DE69013760T2 (de)
FI (1) FI902209A0 (de)
FR (1) FR2646671B1 (de)
IL (1) IL94250A0 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2661416A1 (fr) * 1990-04-27 1991-10-31 Rhone Poulenc Chimie Materiau organique eventuellement oriente, actif en optique non lineaire et son procede d'obtention.
JP2813925B2 (ja) * 1990-07-06 1998-10-22 日本電信電話株式会社 有機光非線形材料および非線形素子
EP0550105A3 (en) * 1991-12-30 1993-11-18 Akzo Nv Liquid-crystalline polyurethanes, compositions of said liquid-crystalline polyurethanes, and a device for optical data storage comprising a liquid-crystalline polyurethane
CA2139671A1 (en) * 1992-07-06 1994-01-20 Bernardus Hendrikus Maria Hams Non-linear optiically active polyurethanes having high glass transition temperatures
FR2706900B1 (de) * 1993-06-25 1995-09-08 Flamel Tech Sa
DE4335541A1 (de) * 1993-10-19 1995-04-20 Basf Ag Azo- oder Stilbenfarbstoffgruppierungen und Urethangruppen enthaltendes Polyaddukt und dessen Verwendung in der nicht-linearen Optik
US5486580A (en) * 1994-11-02 1996-01-23 The Dow Chemical Company Mesogenic novolacs and resins
US5514770A (en) * 1995-04-18 1996-05-07 Ansong; Omari Sulfides of nitroamino triphenyl and substitution or amino functionalized products thereof and the method of preparing the same
AU2003304679A1 (en) * 2002-12-09 2005-06-08 Rensselaer Polytechnic Institute Nanotube-organic photoelectric conversion devices and methods of making same
AU2003297685A1 (en) * 2002-12-10 2004-06-30 Rensselaer Polytechnic Institute Nanotube based non-linear optics and methods of making same
EP2380244B1 (de) 2008-12-16 2015-09-23 Delphi International Operations Luxembourg S.à r.l. Kurzschluss-clip für ein airbag-zündsystem

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63175837A (ja) * 1987-01-16 1988-07-20 Nippon Telegr & Teleph Corp <Ntt> 有機非線形光学材料

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL237188A (de) * 1959-01-22
DE2426172C3 (de) * 1974-05-29 1978-07-27 Bayer Ag, 5090 Leverkusen Verfahren zum Färben von Polyurethankunststoffen
JPS6041950B2 (ja) * 1981-09-04 1985-09-19 旭硝子株式会社 抗凝血性材料
US4603187A (en) * 1985-03-11 1986-07-29 Celanese Corporation Polyacetylenic compositions
AT385040B (de) * 1985-03-15 1988-02-10 Lim Kunststoff Tech Gmbh Verfahren zur herstellung von polyurethanen, insbesondere von polyurethanelastomeren, sowie verfahren zur radikalischen polymerisation
US4859876A (en) 1985-09-16 1989-08-22 AT&T Bell Laboratories American Telephone and Telegraph Company Nonlinear optical materials and devices
JPH0739457B2 (ja) * 1986-05-14 1995-05-01 タキロン株式会社 両親媒性セグメントポリウレタン
DE3628141A1 (de) * 1986-08-19 1988-02-25 Bayer Ag Lineare polyurethan-elastomere und verfahren zu ihrer herstellung
DE3636972A1 (de) * 1986-10-30 1988-05-05 Bayer Ag Harnstoff-gruppen enthaltende diole und daraus hergestellte polyurethanelastomere
US4757130A (en) * 1987-07-01 1988-07-12 Hoechst Celanese Corporaton Condensation polymers with pendant side chains exhibiting nonlinear optical response
FR2636745B1 (fr) * 1988-09-16 1990-11-09 Rhone Poulenc Chimie Polymeres et materiaux les contenant, actifs en optique non lineaire, procedes de fabrication de ces polymeres et materiaux et dispositif optoelectrique les contenant
US4983482A (en) * 1989-04-03 1991-01-08 Xerox Corporation Photoconductive imaging members with polyurethane hole transporting layers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63175837A (ja) * 1987-01-16 1988-07-20 Nippon Telegr & Teleph Corp <Ntt> 有機非線形光学材料

Also Published As

Publication number Publication date
FI902209A0 (fi) 1990-05-02
JPH0832760B2 (ja) 1996-03-29
DE69013760D1 (de) 1994-12-08
JPH03121114A (ja) 1991-05-23
FR2646671B1 (fr) 1993-01-22
FR2646671A1 (fr) 1990-11-09
CA2015923A1 (fr) 1990-11-03
US5075409A (en) 1991-12-24
EP0401063A1 (de) 1990-12-05
IL94250A0 (en) 1991-03-10
DE69013760T2 (de) 1995-03-09
ATE113623T1 (de) 1994-11-15

Similar Documents

Publication Publication Date Title
EP0359648B1 (de) Polyurethane mit nichtlinearen optischen Eigenschaften und diese enthaltende Materialien, diese enthaltende optische Vorrichtung und Verfahren zur Herstellung dieser Verbindungen und Materialien
EP0401063B1 (de) Polymere mit nichtlinearer optischer Aktivität
EP0363237B2 (de) Polymere und daraus hergestellte Materialien, mit nichtlinearen Eigenschaften, Verfahren zu deren Herstellung und daraus hergestellte optoelektrische Materialien und Gegenstände
EP0724747B1 (de) Polyesterimide verwendbar in linearer und/oder nichtlinearer optik und verfahren zu deren herstellung
US5433895A (en) Silicon-containing networked non-linear optical compositions
EP0705289B1 (de) Vernetzbares polymer, insbesondere verwendbar in der optik und in der nichtlinearen optik, daraus hergestellte materialien und gegenstände und verfahren zur herstellung dieses polymers
FR2825480A1 (fr) Polyimides pour ancrage de cristaux liquides, dispositifs d&#39;affichage les incluant et procede de preparation de ces dispositifs
FR2668158A1 (fr) Polymere reticulable pour applications en optique non lineaire.
EP0641808B1 (de) Vernetzbares Polymer verwendbar in nicht linearen optischen Vorrichtungen und Verfahren zu seiner Herstellung
US5275924A (en) Amphiphilic compounds for sequential monolayer deposition
JP2000128983A (ja) 非線形光学活性コポリマ―及びこの種のコポリマ―を含む電気光学及び光デバイス
FR2661416A1 (fr) Materiau organique eventuellement oriente, actif en optique non lineaire et son procede d&#39;obtention.
FR2657083A1 (fr) Polyesters actifs en optique non lineaire et materiaux les contenant dispositif optique les contenant et procedes de fabrication de ces composes et materiaux.
EP0478480A1 (de) Monomere, Polymere und sich davon ableitende, gegebenenfalls orientierte Materialien für die nichtlineare Optik und Verfahren zur Herstellung
FR2819892A1 (fr) Procede d&#39;obtention d&#39;un materiau electro-optique et solution de polyimides pour la mise en oeuvre du procede
EP0436708A1 (de) In der nichtlinearen optik verwendbare orientierbare blockcopolymere
FR2650283A1 (fr) Copolymeres sequences presentant une activite en optique non lineaire
Guenthner et al. Polyimides with attached chromophores for improved performance in electro-optical devices
JPH0580277A (ja) 光非線形主鎖型高分子材料
JPH08501811A (ja) 高いガラス転移温度を有する非線形光学活性ポリウレタン
Lee et al. Organic-inorganic hybrid materials for nonlinear optics applications
Kamath et al. Second-order nonlinear optical properties of a polymer exhibiting optical transparency down to 340 nm
FR2721937A1 (fr) Polymers onl reticules, procede pour leur preparation et pour leur utilisation
JPH07508992A (ja) 非線形光学特性を有するポリエン
EP0415816A1 (de) Polymere mit nichtlinearen optischen Eigenschaften

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19910202

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FLAMEL TECHNOLOGIES

17Q First examination report despatched

Effective date: 19920925

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19941102

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19941102

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19941102

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19941102

Ref country code: DK

Effective date: 19941102

REF Corresponds to:

Ref document number: 113623

Country of ref document: AT

Date of ref document: 19941115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69013760

Country of ref document: DE

Date of ref document: 19941208

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19941215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19950202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19950430

Ref country code: LI

Effective date: 19950430

Ref country code: BE

Effective date: 19950430

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19950430

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
BERE Be: lapsed

Owner name: FLAMEL TECHNOLOGIES

Effective date: 19950430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960328

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960419

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960422

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19971101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971101

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20030423

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST